Process for the preparation of polyorganosilylated carboxylate monomers or polymers thereof

Abstract

The present invention relates to polyorganosilylated carboxylate monomers or polymers thereof, comprising a polyorganosilylated carboxylate monomer of the general formula (I) or a polymer thereof, wherein R1, R2, R3, R4, R5 each independently represent hydrogen, alkyl, alkenyl, alkynyl, alkyloxy, aryl, aralkyl or halogen radical optionally substituted by one or more substituents independently selected from the group comprising alkyl, aralkyl, aryl, hydroxy, halogen, amino or amino alkyl radicals, R7 represents hydrogen, alkyl radical or —COOR9, wherein R9 represents an alkyl group, R8 represents hydrogen, alkyl radical or —CH2—CO2—(SiR4R5O)n—SiR1R2R3, and n represents a number of dihydrocarbylsiloxane units from 3 to 20. The invention also relates to the use of these monomers or polymers as coating compositions including antifouling coating compositions.

Description

CROSS-REFERENCE TO OTHER APPLICATION [0001] This application is a continuation of and claims priority to pending U.S. application Ser. No. 10 / 520,636 filed on Aug. 5, 2005 under 35 § U.S.C. 371. Application Ser. No. 10 / 520,636 is the national phase of PCT International Application No. PCT / EP2003 / 007360 filed on Jul. 9, 2003, which in turn claims priority to European Patent Application No. 02254861.4, filed Jul. 10, 2002, and European Patent Application No. 02255549.4, filed Aug. 8, 2002. The entire contents of each of the above-identified applications are hereby incorporated by reference.FIELD OF THE INVENTION [0002] The invention relates to an improved method for the preparation of polyorganosilylated carboxylate monomers or polymers. The invention further relates to said obtained polyorganosilylated carboxylate monomers or polymers and in another aspect, the invention relates to their use for the synthesis of hydrolysable polymers, such as binders for modern antifouling coatings. ...

AI Technical Summary

Benefits of technology

[0052] Still another advantage of the invention is that the polyorganosilylated carboxylate monomers or polymers obtained by the process according to the invention have the exactly desired number of dihydrocarbylsilyloxy units.

[0053] The polyorganosilylated carboxylate monomers obtained by the process of the invention can be polymerised with various other monomers such as vinyl monomers including acrylic esters, methacrylic esters, styrene, vinyl esters (e. g. , vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate), vinyltoluene, alpha-methylstyrene, crotonic esters, and itaconic esters.

[0054] The polymers and copolymers of said monomers are useful in coating or paint composition. More preferably they are used as comonomer unit in the binder of antifouling coating compositions. When used in an antifouling coating composition, they give a film which undergoes neither cracking nor peeling and shows moderate hydrolysability to dissolve into seawater constantly at an adequate rate and which therefore exhibits excellent antifouling property for long term.

[0055] The antifouling coating compositions prepared using the monomers obtained by the process of the invention are tin-free coatings and provide an alternative to the present self-polishing coating technology based on hydrolysable tributyltin polymers (the use of which is due to be banned in antifouling paints by 2003). The polyorganosilylated carboxylate monomers provided by the process of the invention compared to organotin compounds are less toxic, less polar, more hydrophobic and more stable.

[0056] The invention will be more readily understood by reference to the following examples, which are included merely for purposes of illustration of certain aspects and embodiments of the present invention and are not intended to limit the invention.

[0057] Examples In the following examples, NMR data have been determined in CDC13 and are expressed as delta versus TMS. Unless otherwise stated, all the reactants were purchased from Aldrich and were used without purification.

Problems solved by technology

When such aquatic organisms adhere and propagate on an underwater structure like the bottom of a ship, the surface roughness of the whole ship may be increased to induce decrease of velocity of the ship and subsequently increase of fuel consumption.

The removal of these aquatic organisms from the ship's bottom requires much labour and a long period of working time.

In addition, if these aquatic organisms adhere and propagate on an underwater structure such as a steel structure they deteriorate their anticorrosive coating films leading to a reduction of the lifetime of the underwater structure.

This process has disadvantages such as the reduced availability and storage stability of the silyl chloride.

Moreover, the reaction yields as a by-product a hydrogen halide, which provokes the corrosion of the production equipment, or a halide salt, which has to be removed by filtration.

This method has the disadvantage of producing ammonia.

One of the disadvantages of this method is the risk of hydrogenation of the unsaturated carboxylic acid due to a side reaction of the produced H2 on the carbon-carbon double bond.

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